Modifiers for synthetic resin molding compositions and process of producing the same



Patented May 5, 1953 UNITED STATES PATENT OFFICE MODIFIERS FOR SYNTHETICRESIN MOLD- ING ooMrosrrlous: AND PRocass-or raonoom 'rnn sAMEw 1 nTzeng iueu Su'en' and Arthur M. Schiller, Stam- Mains,

ford, Conn, assignors to AmericanyCyanamid Company, New York, N. Y., acorporation of '5 Claims. (obese-30.4)

This invention relates to novel molding comp tiqnycq r ins ur o adehyde: ins mgl'dsQW-W t el ea ducts of an epihalohi fi l-wi h 11a ,mcpsl r e h of :a :d m' nv st reig ht chain aliphatic alcohol; wherein-said monoalkyl ether ,ofgm diprimary straight, chain rchalnalcoholcontains betweem 1- 6 alkylepeoxy; groups; inclusive; of which; eachalkyleneoxy group contain s 2-6 carbon atoms and wherein said' alkylgroup is selected from methyl and ethyl alcohol. ."This inventionfurtherrelates to the processof preparing the reaction product of: anepihaloh-ydrin :with' a monoalkyl awg diprimarystraight-ohain aliphaticalcohol under alkaline; conditions; This invention furjtherrelates tothe-use of the above-identified reaction products which have beenpreparedundegalkaline conditions. "The modifiers for the urea resins area group of compounds having the general formula;

One of the objects oi the present nvention is to use thereactionproductsdefined herelnahove as modifiers in urea-formaldehyde,ngolding powders whereby the shrinkage of, articles molded with saidpowders is reduced, to a considerable. and

-d r and W Q IQPS. he iel o appli az tion ofurea-formaldehyde moldingcompositions, is' consideraoly enlarged. A further object of thepresentinvention is to use the reactionproducts defined hereinabove asflow promoters for resinous compositions such as urea-iormaldehyderesinshmlamine-formaldehyde resins and the like. A'further object of thepresent invention is'to use as modifiers' for resinsthe substitutedpro-panes. having the general formula:

is -i a wherein R, is a member of the group methyl and ethylm isan-integerbetween 2-6,'inclusive,-and

maisan integerbetween-b6. inclusive. These and other objects of thepresent invention will be discussed in greater'detail hereinbelow;

Attention is directed to the copen'ding application 01 one of theco-inventors of thepre's'ent invention, namelyl. J. Suen,whosecope'ndiiig application 'maybeddentified bythe Serial 'l lo.151,035, filed March 21, 1950, now abandoned. In this copendingapplication, there is described andclaimeda process fol-pre aring compouds having the general formula where R is a member of the group methyland ethyL-n is an lntegerbetween 2&6, inclusive,- and mis, anintegenbetween 1+6, inblusiva In the prepanationof reaction productsused to modify the resinsto .producethe compositionsof the presentinvention, one of the components to thereaction is an epihalohydrin, andit is immaterial whichparticular epihalohydrin is selected. Asa.c0nsequence, one may use epichlorohydrin, epibromohydrin,epiiodohydrin, or epifluorohydrin. .,However, as epichlorohydrin isgenerally available,it is preferred.

In the preparation of the reaction products used in thepresentinvention, one may use as a. coreactant with the ep-ihalohydrin, themonomethyl others or the monoethyl ethers of such diprimary straightchain aliphatic alcohols asethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, pentaethylenerglycol,hexaethylene glycol, propanediol-l,3,di(propanediol lfi) structurallyrepresented as tri propanediol 1,3) moicnnmon; hexa(propanediol 1,3,H[O(CH2)3]6OH bu'tanediol- 114; tetra(butanediol 1,4); H[O(CH2)4]4OH;hexa- (butanediol 1,4), H[O(CH2)'4]6OH; pentanediol- 1,5;penta(pentanediol 1,5), H[O(CHal5]s0Hi hexa(pentanediol 1,5),H[O(CH2)5]6OH hxanedial 1,6 di(hexanediol)l,6 H[O(CH2) 5120K:hexa(he'xanediol 1,6), H[0(CH2)6]6OH and the like. It must berememberedjhowe'verf 'that the dip'rima'ry straight chain aliphaticalcohols; 'use'd toform the monomethyl or'monoethyl 'ethe'rs as definedhereinabove, must contain 1-6 alkylen'e oxy groups inclusive, of whicheach alkyleneoxy group contains 2-6 carbon atoms.

In order that the present invention may be completely understood, thefollowing examples are set forth for the purpose of illustration onlyand are not to be interpreted as limitations on the case except asindicated by the appended claims. All parts'are parts by Weight.

3 EXAMPLEI 277.5 parts of epichlorohydrin (3 mols) and 402.6 parts ofthe monoethyl ether of diethylene glycol (3 mols) are introduced into asuitable reaction chamber and mixed together thoroughly whereupon 240parts of a 50% aqueous solution 01' sodium hydroxide (3 mols) isintroduced slowly over a period of about /2 hour with constant stirring.The reaction temperature is maintained below 55 C. with the aid ofexternal cool-- ing. After all the sodium hydroxide has been added, thetemperature is allowed to rise to 80-90 C. in about 5 minutes and ismaintained at this approximate range for about minutes. The reactionproduct is then cooled to room temperature and the salt formed, in thecourse of the reaction, is filtered oil with the aid 01 500 parts ofdioxane. The filtrate is vacuum concentrated under a pressure of 4.55.5centimeters of mercury until the temperature reaches 111 C. During theconcentration, there is still a small amount of salt precipitated out.The salt is again filtered off and the finished product is a clearliquid, reddish in color, and soluble in water.

EXAMPLE 2 1073 parts of diethylene glycol monoethyl ether (8 mols) and740 parts of eplchlorohydrin (8 mols) are introduced into a suitablereaction chamber and thoroughly mixed together whereupon 672 parts of a50% aqueous solution of sodium hydroxide (8.4 mols) is introduced slowlywith constant stirring over a period of 45 minutes. The reactiontemperature is maintained at about 50-60 C. with the aid of externalcooling. After all the sodium hydroxide has been added, the reactionmixture is permitted to warm up to IO-75 C. and maintained at thattemperature for an additional half hour. The mixture is then cooled toroom temperature and neutralized with concentrated hydrochloric acid toa pH of '7. The product is filtered to remove the salt formed and thefiltrate is vacuum concentrated under an absolute pressure of about 50mm. of mercury until the temperature reaches 105 C. The resi due mayagain be filtered to remove any additional salt.

In the filtering step in the examples set forth both hereinabove andhereinbelow, use is made of a particular inert solvent. namely dioxane.It is actually not necessary to use a solvent, but it is preferred touse one, in order to lower the viscosity and for ease in accomplishinthe process. If one elects to use a solvent. one should select an inertsolvent such as an ether of a monohydric alcohol or a diether of adihydric alcohol or a monoaliphatic ester of a monohydric alcohol or apolyester of an aliphatic monocarboxylic acid and a polyhydrlc alcoholsuch as diethyl ether, dipropyl ether, dibutyl ether, methyl propylether, dimethyl ether of ethylene glycol, diethyl ether of ethyleneglycol, dimethyl ether of diethylene glycol. ethyl acetate. ethyleneglycol. diacetate. methoxyethylene glycol acetate and the like.

EXAIVIPLE 3 185 parts of epichlorohydrin (2 mols) and 356 parts oftriethylene glycol monoethyl ether (2 mols) are mixed together in asuitable reaction chamber and 200 parts of a 40% aqueous solution ofhydroxide (2 mols). is slowly added in the course of about minutes,during which time the temperature is maintained at 60 C. or below. Thereaction mixture is then allowed to warm up and is maintained at 80-85C. for a /2 hour period. After the reaction mixture has been cooled, 200parts of dioxane is added and the mixture further cooled to about 10 C.and is filtered to remove the salt formed in the course of the reaction.The filtrate is vacuum concentrated under an absolute pressure of about50 mm. of mercury to a temperature of 115 C. The cooled residue is againfiltered.

EXAMPLE 4 277 parts of eplchlorohydrin (3 mols) and 270 parts ofethylene glycol monoethyl ether (3 mols) are mixed together in asuitable reaction chamber and 300 parts of a 40% aqueous solution ofsodium hydroxide is slowly added over a period of about hour while thetemperature is maintained at 50-55 C. The reaction mixture is thenallowed to warm up and is maintained at 80-85 C. for a. 15 minuteperiod, whereupon the mixture is cooled to room temperature. The mixtureis then filtered to remove the salt formed in the course of the reactionand the filtrate is vacuum concentrated under an absolute pressure ofabout 50 mm. of mercury to a temperature of about C. The cooled residueis again filtered.

EXAMPLE 5 277 parts of eplchlorohydrin (3 mols) and 360 parts ofdiethylene glycol monoethyl ether (3 mols) are mixed together in asuitable reaction chamber and 300 parts of a 40% aqueous solution ofsodium hydroxide (3 mols) is added slowly over a period of about hourwhile the temperature is maintained at about 55 C. or below. Thereaction mixture is then allowed to warm up and is maintained at about80-85 C. for approximately 20 minutes. The reaction product is thencooled to about room temperature and filtered to remove the salt formedin the course of the reaction and the filtrate is vacuum concentratedunder an absolute pressure of about 50 mm. of mercury to a temperatureof about C. The concentrated product is cooled and again filtered.

EXAMPLE 6 1 ,Z-epoxy, 3-ethoxyethory-propane 463 parts 01'eplchlorohydrin (5 mols) and 451 parts of ethylene glycol monoethylether (5 mols) are mixed together in a suitable reaction chamberequipped with thermometer, stirrer, reflux condenser, and droppingfunnel. 675 parts of a solution containing 200 parts of sodium hydroxide(5 mols) in water is slowly added in about a 15 minute period. Thetemperature of the reaction mixture is maintained at about 28-31 C. Thereaction is permitted to proceed at 28-31 C. for about 7% hours. At thispoint, titration of a sample of reaction mixture indicates that about60% of the cautic has been reacted. When stirring is stopped, thereaction mixture separates into an organic layer, an aqueous layer, anda salt layer. The organic layer is removed and fractionated under vacuumwith a suitable fractionating column. After removing the unreactedreagents and stirring, the 1,2- epoxy, 3-ethoxyethoxy-propane iscollected at 60-65 C. under an absolute pressure of 4 mm. of mercury.The yield amounts to about 260 parts.

It has been stated hereinabove that the condensation products of thepresent invention may be utilized as modifiers for synthetic resinousmolding compositions such as urea-formalde hyde molding'powders,particularly jm r;

90sec; reducing .theamountof shrinkag pi the article's moldecljwiththese molding powders. The following example is se tfforth to illustratehow this may be accomplished.

EXAMPlE-E'l I} fifeatffbrrhaldehyd resin syrup infthe' conventional waywith .amglratio of formaldehyde to tires. of 1.3351 in theate actionbetween the, formaldehyde eseggeei carried dut' at alfDH or about'Liland at .a tgm peratui'eof about 30 C. for l nem'..,1,: rms' e..

tion is continued at 50 C. until free formaldehyde contnt drops to about4.5%. The diethylene glycol monoethyl ether-epichlorohydrin condensationproduct prepared as descrihedin. Example 1 hereinabove may, be added asa Q9 11 fie'r, a resin syrup such 'as the. one .prepared herelhabove andthe pH of the solution is ad-U age to be 4.5 niils per'inch and age 1.2mils perinch. An unmodified molding powder'js'hows af'rhold shrinkageaveraging 4-6 mils 'perinen and after shrinkage averaging 4-7 mils perinch. i 5,.

The determination of the shrinkage of a molded article is accomplishedin the following manner. The shrinkage of the molded article isevaluated by means of a test piece in the form of a circular disk inchthick and 4 inches in diameter and is measured in terms of moldshrinkage" and after shrinkage. If the diameter of the cold mold cavityis denoted as A; the diameter of the molded disk after being conditionedat C. and at a relative humidity of 50% for 48 hours is denoted as B;and the diameter of the disk after further conditioning for 48 hours at220 F. and thereafter being cooled to 25 C. at 50% relative humidity isdenoted as C, the following equations can be set up in which theshrinkages are measured in terms of mils/ inch Mold shrinkage= i x 1000After shrinkage= Total ehrinke e= i x 1000 EXAMPLE 8 EXAMPLE 9 Aurea-formaldehyde molding powder moditied with the condensation productprepared according to the process of Example 2 is prepared in the samemanner as that set forth in Example '7 except that the resinsolids:modiiier:pulp ratio is 55:10:35. Upon evaluation the moldshrinkage is 4.4mm perinch and the after shrinkage 0.9 mils per inch.

.u rm A ureadormaldehydelmolding powder modified h-the Pm mnr paredaccording to the proce a .QLE mP 13. is-ur pared according to theprocedure set forth hereinabove according to Example 'll lponevaluation, its mold shrinkage is 4.5 mils per inchand its aftershrinkage 1.5 mils per inch.

' "EXALEPLE 11" Al-ure a-formaldehyde molding powder, modi-:.: fied.with,the product, prepared according to Exe. ample .4, js.preparedaccording to the procedure.

hereipahoveunder Example fl. Upon evalution,

, the mold shrinkage is 4-5 mils per inch and the after shrinkage is 1.3mils per inch.

EXAMPLE 12 A urea-formaldehyde molding powder modie fied with theproduct prepared according to Example 5 is ,tormulated according to theproce-.

dure as .set fprth hereinabove in Example ,7...

Upon evaluation, the mold shrinkage is 4.5 mils per inch. and the aftershrinkage 1.4 mils per inch.

In addition to compoun snavm the general formula as defined hereihabove,

present in the condensation products of the present invention, there arealso present compounds having the general formula:

and the like, where K R[O(CI'I2)n]m and n is an integer between 2-6inclusive, and m is an integer between l-S, inclusive, R is a member ofthe group methyl and ethyl.

The yield of the l,Z-epoxy-3-alkoxyalkylene oxy propane is notparticularly substantial in the practice of the process of the presentinvention. In the practice of the process of the copending applicationof T. J. Suen, identified hereinabove. the yield is substantiallyimproved. The condensation products of the present invention have,however, a greater efiect on the reduction of shrinkage of moldedarticles than have the substituted propanes used individually and havingthe general formula:

wherein R is a member of the group methyl and ethyl, n is an integerbetween 2-6, inclusive, and m is an integer between 1-6, inclusive.Obviously, these modifiers can be used with ureaformaldehyde moldingpowders having mol ratios different from the 1:1.33 set forthhereinabove such as 1:1 to 1:4. These modifiers can be used 7additionally to modify other resinous molding compositions such asmelamine-formaldehyde resins, guanadine resins, phenolic resins, anilineresins and the like.

Included in the group of specific compounds which the applicants havediscovered are the following: 1,2 -epoxy. S-methoxyethoxy-propane;l,2-epoxy, 3-ethoxyethoxy-propane; 1,2-epoxy, 3methoxyethoxyethoxy-propane; 1,2 epoxy. 3 ethoxyethoxyethoxy propane;1,2 epoxy. 3 methoxyethoxyethoxyethoxyethoxyethoxy ethoxy-propane:1,2-epoxy, 3-ethoxyethoxyethoxyethoxyethoxyethoxyethoxy propane; 1,2-epoxy, 3-methoxypropoxy-propane; 1,2-epoXy, 3 ethoxypropoxy propane; 1,2epoxy, 3 inethoxypropoxypropoxypropoxypropoxypropoxypropoxy propane;1,2-epoxy, 3-ethoxypropoxypropoxypropoxypropoxypropoxypropoxy pro pane;1,2-epoxy, 3-methoxybutoxy-propane; 1.2- epoxy, S-ethoxybutyoxy propane;1,2-epoxy. 3 methoxybutoxybutoxybutoxybutoxybutoxybutoxy propane; 1,2epoxy, 3 ethoxybutoxybutoxybutoxybutoxybutoxybutoxy-propane; 1,2- epoxy,B-methoxypentoxy-propane; 1,2-epoxy, 3 ethoxypentoxy propane; 1,3 epoxy,3 methoxypentoxypentoxypentoxypentoxypentoxypentoxy-propane; 1,2-epoxy,B-ethoxypentoxypentoxypentoxypentoxypentoxypentoxy propane; 1,2-epoxy,3-rnethoxyhexoxypropane; 1,2- epoxy, 3 ethoxy hexoxy propane; 1,2 epoxy,3 methoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy-propane; 1,2-epoxy,3-ethoxyhexoxyhexoxyhexoxyhexoxyhexoxyhexoxy-propane.

This case is a division of application, Serial No. 151,031, filed March21, 1950, which relates to 8 the substituted propanes definedhereinabove and the process of preparing the same.

We claim:

1. A molding composition comprising a ureaformaldehyde resin and theheat reaction product of an epihalohydrin with a compound having thegeneral formula: HlO(CH2)nlmOR, wherein R is a member selected from thegroup consisting of methyl and ethyl, n is an integer between 2-6,inclusive, and m is an integer between 1-6 inclusive, wherein saidreaction product is produced under alkaline conditions.

2. A molding composition comprising a ureaformaldehyde resin and acompound having the general formula:

wherein R is a member selected from the group consisting of methyl andethyl, n is an integer between 2-6, inclusive, and m is an integerbetween 16, inclusive.

3. A molding composition comprising a ureaformaldehyde resin and1,2-epoxy, 3-methoxyethoxy-propane.

41 A molding composition comprising a ureaformaldehyde resin andi,2-epoxy, B-ethoxyethoxy-propane.

5. A molding composition comprising a urea formaldehyde resin and1,2-epoxy, 3-ethoxyethoxyethoxy-propane.

TZENG JIUEQ SUEN. ARTHUR M. SCHILLER.

No references cited.

1. A MOLDING COMPOSITIION COMPRISING A UREAFORMALDEHYDE RESIN AND THEHEAT REACTION PRODUCT OF AN EPIHALOHYDRIN WITH A COMPOUND HAVINGG THEGENERAL FORMULA: H(O(CH2)N)MOR, WHEREIN R IS A MEMBER SELECTED FROM THEGROUP CONSISTING OF METHYL AND ETHYL, N IS AN INTEGER BETWEEN 2-6,INCLUSIVE, AND M IS AN INTEGER BETWEEN 1-6 INCLUSIVE, WHEREIN SAIDREACTION PRODUCT IS PRODUCED UNDER ALKALINE CONDITIONS.